EP2882835B1 - Liquid compositions free of alkanolamine comprising surfactants - Google Patents

Description

The invention relates to liquid compositions containing a high total concentration of anionic and nonionic surfactants but free from alkanolamines and their salts. The liquid compositions can be used to wash and clean textiles and, in combination with bleaching systems, provide beneficial bleaching performance.

Liquid detergents are enjoying a rapidly increasing popularity in the market, because they can be dosed easily and without dust development, quickly release the washing-active ingredients during washing and also leave no residues on the laundry. In recent years, a trend towards increasingly concentrated liquid detergents has become established in order to be able to produce small, easy-to-handle packaging units and to reduce transport costs.

The preparation of highly concentrated liquid detergents necessitates the use of highly soluble surfactants, hydrotropes and solvents. Very widespread in such products is the use of anionic surfactants in the form of their highly soluble ethanolamine salts and also the use of ethanolamines as a solvent.

In DE 19511192 . EP 0490436 . WO 92/20769 . DE 102004043728 . DE 4216453 . DE 4023893 . US 3,998,750 describes alkanolamine-free detergents comprising mixtures of anionic and nonionic surfactants.

A major disadvantage of liquid detergents is their low compatibility with bleach systems and, as a result, their poor wash performance on bleachable soils.

It was therefore an object to provide concentrated compositions, in particular with high surfactant content, which in the application with Bleach systems allow an advantageous removal of bleachable stains during washing.

1. a) ein oder mehrere anionische Tenside ausgewählt aus der Gruppe bestehend aus den Tensidklassen der Sulfonate, Sulfate, Carboxylate und Phosphate und die Gegenionen der anionischen Tenside der Komponente a) ausgewählt aus der Gruppe bestehend aus den Kationen von Natrium, Kalium, Calcium und Magnesium, und
2. b) ein oder mehrere nichtionische Tenside ausgewählt aus der Gruppe bestehend aus den Tensidklassen der alkoxylierten Fettalkohole, Fettsäureamide, alkoxylierten Fettsäureamide und Alkylpolyglykoside,

dadurch gekennzeichnet, dass sie die Tenside der Komponenten a) und b) in einer Gesamtkonzentration von > 50 Gew.-%, bezogen auf das Gesamtgewicht der flüssigen Zusammensetzungen, enthalten, und wobei die anionischen Tenside der Komponente a) und die nichtionischen Tenside der Komponente b) in der flüssigen Zusammensetzung in einem Gewichtsverhältnis von Komponente a) zu Komponente b) von 3 zu 1 bis 1 zu 3 vorliegen, und frei sind von Alkanolaminen und deren Salzen.Surprisingly, it has been found that this object is achieved by liquid compositions having a viscosity of from 100 to 20 000 mPas, measured using the Brookfeld LVT-II viscosimeter at 20 revolutions / minute and at 20 ° C., containing

1. a) one or more anionic surfactants selected from the group consisting of the surfactant classes of sulfonates, sulfates, carboxylates and phosphates and the counterions of the anionic surfactants of component a) selected from the group consisting of the cations of sodium, potassium, calcium and magnesium, and
2. b) one or more nonionic surfactants selected from the group consisting of the surfactant classes of the alkoxylated fatty alcohols, fatty acid amides, alkoxylated fatty acid amides and alkyl polyglycosides,

characterized in that they contain the surfactants of components a) and b) in a total concentration of> 50 wt .-%, based on the total weight of the liquid compositions, and wherein the anionic surfactants of component a) and the nonionic surfactants of the component b) are present in the liquid composition in a weight ratio of component a) to component b) of 3 to 1 to 1 to 3, and are free from alkanolamines and their salts.

1. a) ein oder mehrere anionische Tenside ausgewählt aus der Gruppe bestehend aus den Tensidklassen der Sulfonate, Sulfate, Carboxylate und Phosphate und die Gegenionen der anionischen Tenside der Komponente a) ausgewählt aus der Gruppe bestehend aus den Kationen von Natrium, Kalium, Calcium und Magnesium, und
2. b) ein oder mehrere nichtionische Tenside ausgewählt aus der Gruppe bestehend aus den Tensidklassen der alkoxylierten Fettalkohole, Fettsäureamide, alkoxylierten Fettsäureamide und Alkylpolyglykoside,

wobei die Gesamtmenge an Tensiden der Komponenten a) und b) > 50 Gew.-% beträgt, bezogen auf das Gesamtgewicht der flüssigen Zusammensetzung, und wobei die anionischen Tenside der Komponente a) und die nichtionischen Tenside der Komponente b) in der flüssigen Zusammensetzung in einem Gewichtsverhältnis von Komponente a) zu Komponente b) von 3 zu 1 bis 1 zu 3 vorliegen, mit der Maßgabe, dass die Zusammensetzung frei ist von Alkanolaminen und deren Salzen,
in Gegenwart eines oder mehrerer Bleichmittel zum Reinigen von Textilien.Accordingly, an object of the present invention is the use of a liquid composition having a viscosity of from 100 to 20,000 mPas, as measured by the Brookfield LVT-II viscometer at 20 revolutions / minute and at 20 ° C

1. a) one or more anionic surfactants selected from the group consisting of the surfactant classes of sulfonates, sulfates, carboxylates and phosphates and the counterions of the anionic surfactants of component a) selected from the group consisting of the cations of sodium, potassium, calcium and magnesium, and
2. b) one or more nonionic surfactants selected from the group consisting of the surfactant classes of the alkoxylated fatty alcohols, fatty acid amides, alkoxylated fatty acid amides and alkyl polyglycosides,

wherein the total amount of surfactants of components a) and b) is> 50 wt .-%, based on the total weight of the liquid composition, and wherein the anionic surfactants of component a) and the nonionic surfactants of component b) in the liquid composition in a weight ratio of component a) to component b) of 3 to 1 to 1 to 3, with the proviso that the composition is free of alkanolamines and their salts,
in the presence of one or more bleaches for cleaning textiles.

1. a) ein oder mehrere anionische Tenside ausgewählt aus der Gruppe der sekundären Paraffinsulfonaten und die Gegenionen der anionischen Tenside der Komponente a) ausgewählt aus der Gruppe bestehend aus den Kationen von Natrium, Kalium, Calcium und Magnesium, und
2. b) ein oder mehrere nichtionische Tenside ausgewählt aus der Gruppe bestehend aus den Tensidklassen der alkoxylierten Fettalkohole, Fettsäureamide, alkoxylierten Fettsäureamide und Alkylpolyglykoside,

dadurch gekennzeichnet, dass sie die Tenside der Komponenten a) und b) in einer Gesamtkonzentration von > 50 Gew.-%, bezogen auf das Gesamtgewicht der flüssigen Zusammensetzungen, enthalten und wobei die anionischen Tenside der Komponente a) und die nichtionischen Tenside der Komponente b) in der flüssigen Zusammensetzung in einem Gewichtsverhältnis von Komponente a) zu Komponente b) von 3 zu 1 bis 1 zu 3 vorliegen, und frei sind von Alkanolaminen und deren Salzen, und
wobei die flüssige Zusammensetzung 5-20 Gew.-% ein oder mehrerer Bleichmittel aus der Gruppe Wasserstoffperoxid und anorganischer Persalze, bezogen auf das Gesamtgewicht der flüssigen Zusammensetzung, enthält.Another object of the invention are liquid compositions having a viscosity of 100 to 20,000 mPas, measured with the Brookfield LVT-II at 20 revolutions / minute and at 20 ° C, containing

1. a) one or more anionic surfactants selected from the group of secondary paraffin sulfonates and the counterions of the anionic surfactants of component a) selected from the group consisting of the cations of sodium, potassium, calcium and magnesium, and
2. b) one or more nonionic surfactants selected from the group consisting of the surfactant classes of the alkoxylated fatty alcohols, fatty acid amides, alkoxylated fatty acid amides and alkyl polyglycosides,

characterized in that they contain the surfactants of components a) and b) in a total concentration of> 50 wt .-%, based on the total weight of the liquid compositions, and wherein the anionic surfactants of component a) and the nonionic surfactants of component b ) in the liquid composition in a weight ratio of component a) to component b) of 3 to 1 to 1 to 3, and are free from alkanolamines and their salts, and
wherein the liquid composition contains 5-20% by weight of one or more bleaching agents selected from the group consisting of hydrogen peroxide and inorganic persalts, based on the total weight of the liquid composition.

When combined with bleach systems, the compositions exhibit significantly higher bleaching performance than comparable alkanolamine-containing compositions.
For the purposes of the present invention, "liquid" compositions are understood to mean all liquid or flowable administration forms. Liquid or flowable in the context of the present invention are compositions which are pourable. The viscosity can be measured by standard methods (for example Brookfield LVT-II at 20 revolutions / minute and 20 ° C.), the spindle 2 being used for the viscosity range 5 to <1000 mPas, the spindle 3 for 1000 to <5000 mPas, spindle 4 is used for 5000 to <10 000 mPas and spindle 7 for 10 000 to 60 000 mPas.
The liquid compositions used according to the invention have viscosities of from 100 to 20,000 mPas, more preferably from 300 to 10,000 mPas, and especially preferably from 400 to 5,000 mPas.
The compositions used according to the invention may be gel-like or paste-like, they may be present as homogeneous solutions or as suspensions, they may be sprayable, be presented in so-called pouches or be made up in otherwise customary dosage forms. The compositions used in the invention contain one or more anionic surfactants selected from the group consisting of the surfactant classes of sulfonates, sulfates, carboxylates and phosphates and more preferably contain one or more anionic surfactants selected from the group consisting of the surfactant classes of sulfonates, sulfates and carboxylates , The counterions of the anionic surfactants are the cations of sodium, potassium, calcium and magnesium.
The compositions used according to the invention are free from alkanolamines and their salts. This means, for example, that this Substances also do not come as counterions of anionic surfactants into consideration.

Preferred sulfonates are secondary paraffin sulfonates. Secondary paraffin sulfonates are surfactants which, statistically distributed, predominantly contain an SO ₃ X group in the secondary position on the paraffin hydrocarbon chain and, to a lesser extent, two or more SO ₃ X groups in the secondary position on the paraffin hydrocarbon chain (X = counterion). The paraffin hydrocarbon chains are predominantly linear and only a minor proportion of 5% by weight or less branched paraffin chains having 8 to 22 carbon atoms. Especially preferred are secondary paraffin sulfonates having 13 to 17 carbon atoms in the paraffin group.

Preference is furthermore given to primary sulfonates, preferably alkane or alkene sulfonates, where the alkyl or alkenyl group can be either branched or linear and optionally substituted by one hydroxyl group. The preferred primary sulfonates contain linear alkyl or alkenyl chains of 9 to 25 carbon atoms, preferably 10 to 20 carbon atoms, and more preferably 13 to 17 carbon atoms.

Likewise preferred are olefin sulfonates which are obtained by sulfonation of C ₁₂ -C ₂₄ -, preferably C ₁₄ -C ₁₆ -α-olefins with sulfur trioxide and subsequent neutralization. Due to the preparation process, these olefin sulfonates may contain minor amounts of hydroxyalkanesulfonates and alkanedisulfonates.

Also preferred are alkenyl or alkylbenzenesulfonates. The alkenyl or alkyl group may be branched or linear and optionally substituted with a hydroxyl group. The preferred alkyl benzene sulfonates contain linear alkyl chains of 9 to 25 carbon atoms, and preferably 10 to 13 carbon atoms.

worin R¹ einen C₈-C₂₀-Kohlenwasserstoffrest, bevorzugt Alkyl, und R einen C₁-C₆ Kohlenwasserstoffrest, bevorzugt Alkyl, darstellt. M steht für ein Kation, das ein wasserlösliches Salz mit dem Estersulfonat bildet.
Besonders bevorzugt sind Methylestersulfonate, in denen R¹ C₁₀-C₁₆-Alkyl und R Methyl bedeutet.Likewise preferred are ester sulfonates of the formula (1)

wherein R ^{1 is} a C ₈ -C ₂₀ hydrocarbon radical, preferably alkyl, and R is a C ₁ -C ₆ hydrocarbon radical, preferably alkyl. M is a cation that forms a water-soluble salt with the ester sulfonate.
Particularly preferred are methyl ester sulfonates in which R ^{1 is} C ₁₀ -C ₁₆ -alkyl and R is methyl.

Preferred sulfates are water-soluble salts of the formula ROSO ₃ M, wherein R is a C ₁₀ -C ₂₄ -Kohtenwasserstoffrest, preferably an alkyl or hydroxyalkyl radical C ₁₀ -C ₂₀ -alkyl component, more preferably a C ₁₂ -C ₁₈ alkyl or hydroxyalkyl radical. M is sodium, potassium, calcium, magnesium or a mixture thereof.

Preferred ether sulfates are water-soluble salts of the linear formula RO (A) _m SO ₃ M, wherein R is an unsubstituted C ₁₀ -C ₂₄ -hydrocarbon radical, preferably C ₁₀ -C ₂₄ -alkyl radical, or a hydroxyl-substituted C ₁₀ -C _24- hydrocarbon radical, preferably a C ₁₀ -C ₂₄ -hydroxyalkyl radical, particularly preferably a C ₁₂ -C ₂₀ -alkyl or hydroxyalkyl radical, particularly preferably a C ₁₂ -C ₁₈ -alkyl or hydroxyalkyl radical. A is an ethoxy (EO) or propoxy (PO) unit, m is a number greater than 0, preferably between 0.5 and 6, more preferably between 0.5 and 3 and M is a cation such as. As sodium, potassium, calcium, magnesium or a mixture thereof.

Particularly preferred are C ₁₂ to C ₁₈ fatty alcohol ether sulfates, wherein the content of EO is 1, 2, 2.5, 3 or 4 moles per 1 mole of the fatty alcohol ether sulfate, and in which M is sodium or potassium.

Further preferred anionic surfactants are carboxylates, in particular. Fatty acid soaps. The soaps may be saturated or unsaturated and may contain various substituents such as hydroxyl groups or α-sulfonate groups. Preferred are linear saturated or unsaturated hydrocarbon radicals as hydrophobic moiety having 6 to 30 and preferably 10 to 18 carbon atoms.

Particular preference is given to the salts of lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, hydrogenated erucic acid, oleic acid, linoleic acid, linolenic acid and mixtures thereof and the salts of fatty acids or fatty acid mixtures of natural fats and oils, preferably of coconut oil, soybean oil, rapeseed oil, sunflower oil , Canola oil, palm fat oil, palm kernel oil, olive oil and tallow fat.

Among the one or more anionic surfactants of component a) of the compositions used according to the invention, the secondary paraffin sulfonates are particularly preferred.

The compositions used according to the invention comprise one or more nonionic surfactants selected from the group consisting of the surfactant classes of the alkoxylated fatty alcohols, fatty acid amides, alkoxylated fatty acid amides, and alkyl polyglycosides.

The alkyl or alkenyl chain of the alkoxylated fatty alcohols may be linear or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms. Particularly preferred are the condensation products of C ₁₀ to C ₂₀ alcohols with 2 to 18 moles of ethylene oxide per 1 mole of alcohol. The alcohol ethoxylates may have a narrow range ("narrow range ethoxylates") or a broad homolog distribution of the ethylene oxide ("Broad Range Ethoxylates"). Examples of commercially available nonionic surfactants of this type are Tergitol® 15-S-9 (condensation product of a linear secondary C ₁₁ -C ₁₅ -alcohol with 9 moles of ethylene oxide), Tergitol® 24-L-NMW (condensation product of a linear primary C ₁₂ -C _14- alcohol with 6 moles of ethylene oxide with a narrow molecular weight distribution). Also included in this product class are the Genapol® brands of Clariant.

worin R eine Alkylgruppe mit 7 bis 21, bevorzugt 9 bis 17 Kohlenstoffatomen ist und jeder Rest R¹ Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Hydroxyalkyl oder (C₂H₄O),H bedeutet, wobei x von 1 bis 3 variiert. Bevorzugt sind C₈-C₂₀-Amide, -monoethanolamide, -diethanolamide und -isopropanolamide.Preference is given to fatty acid amides according to the formula (2)

wherein R is an alkyl group having 7 to 21, preferably 9 to 17 carbon atoms and each radical R ^{1 is} hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl or (C ₂ H ₄ O), H, wherein x varies from 1 to 3. C ₈ -C ₂₀ -amides, -monoethanolamides, -diethanolamides and -isopropanolamides are preferred.

Likewise preferred are alkyl polyglycosides of the formula RO (G) _x , where R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is a glycose unit having 5 or 6 carbon atoms , preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is preferably a number between 1 and 10, more preferably x is between 1.2 and 1.4.

Among the one or more nonionic surfactants of component b) of the compositions according to the invention, the alkoxylated fatty alcohols are particularly preferred.

In addition, surfactants from the group of the polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols can be used. These compounds include the condensation products of alkylphenols having a C ₆ to C ₂₀ alkyl group, which may be either linear or branched, with alkene oxides. These surfactants are used as alkylphenol alkoxylates, e.g. B. Alkylphenolethoxylate called.

R ist hierbei eine Alkyl-, Hydroxyalkyl- oder Alkylphenolgruppe mit einer Kettenlänge von 8 bis 22 Kohlenstoffatomen, R² ist eine Alkylen- oder Hydroxyalkylengruppe mit 2 bis 3 Kohlenstoffatomen oder Mischungen hiervon, jeder Rest R¹ ist eine Alkyl- oder Hydroxyalkylgruppe mit 1 bis 3 Kohlenstoffatomen oder eine Polyethylenoxidgruppe mit 1 bis 3 Ethylenoxideinheiten und x bedeutet eine Zahl von 0 bis 10.Furthermore, water-soluble amine oxides of the formula (3) can be used:

R here is an alkyl, hydroxyalkyl or alkylphenol group having a chain length of 8 to 22 carbon atoms, R ² is an alkylene or hydroxyalkylene group having 2 to 3 carbon atoms or mixtures thereof, each R ¹ is an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms or a polyethylene oxide group having 1 to 3 ethylene oxide units and x represents a number from 0 to 10.

wobei R¹CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff, einen Alkyl oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und Z für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht.It is likewise possible to use polyhydroxy fatty acid amides of the formula (4)

where R ¹ CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and Z is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.

The compositions used according to the invention comprise the surfactants of components a) and b) in a total concentration of> 50% by weight and more preferably of from 50 to 80% by weight, based in each case on the total weight of the compositions according to the invention.

The anionic surfactants of component a) and the nonionic surfactants of component b) in the compositions used according to the invention in a weight ratio of component a) to component b) of 3: 1 to 1: 3, and more preferably 2: 1 to 1: 2 in front.

In addition to the abovementioned anionic and nonionic surfactants, further constituents which may also be used are amphoteric and cationic surfactants, bleaches, bleach activators, bleach catalysts, builders, co-builders, wash alkalis, enzymes, sequestering agents, soil release polymers, grayness inhibitors, dye transfer inhibitors, dye fixing agents, complexing agents, optical agents Whitening, softening components, dyes, fragrances, emulsifiers, hydrotropes, organic solvents, and water in the compositions used.

worin R¹ C₈-C₂₂-Alkyl- oder -Alkenyl, R² Wasserstoff oder CH₂CO₂M, R³ CH₂CH₂OH oder CH₂CH₂OCH₂CH₂CO₂M, R⁴ Wasserstoff, CH₂CH₂OH oder CH₂CH₂COOM, Z CO₂M oder CH₂CO₂M, n 2 oder 3, bevorzugt 2, M Wasserstoff oder ein Kation wie Alkalimetall, Erdalkalimetall, bedeutet.Suitable amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidbetaines, aminopropionates, aminoglycinates or amphoteric imidazolinium compounds according to the formula (5)

wherein R ^{1 is} C ₈ -C ₂₂ alkyl or alkenyl, R ^{2 is} hydrogen or CH ₂ CO ₂ M, R ^{3 is} CH ₂ CH ₂ OH or CH ₂ CH ₂ OCH ₂ CH ₂ CO ₂ M, R ^{4 is} hydrogen, CH ₂ CH ₂ OH or CH ₂ CH ₂ COOM, Z CO ₂ M or CH ₂ CO ₂ M, n is 2 or 3, preferably 2, M is hydrogen or a cation such as alkali metal, alkaline earth metal.

Preferred amphoteric surfactants of this formula are monocarboxylates and dicarboxylates. Examples of these are cocoamphocarboxypropionate, cocoamidocarboxypropionic acid, cocoamphocarboxyglycinate (also referred to as cocoamphodiacetate) and cocoamphoacetate.

Further preferred amphoteric surfactants are alkyl dimethyl betaines and alkyl dipolyethoxy betaines having an alkyl group of 8 to 22 carbon atoms, which may be linear or branched, preferably having 8 to 18 carbon atoms and more preferably having 12 to 18 carbon atoms. These compounds are z. B. marketed by Clariant under the trade name Genagen® LAB.

If the compositions according to the invention contain one or more amphoteric surfactants, these are preferably present in an amount of 0.1-10% by weight and more preferably in an amount of 0.5-5% by weight, based in each case on the Total weight of the compositions according to the invention.

Suitable cationic surfactants are substituted or unsubstituted straight-chain or branched quaternary ammonium salts of the type R ¹ N (CH ₃ ) ₃ ^ρ X ^σ , R ¹ R ² N (CH ₃ ) ₂ ^ρ X ^σ , R ¹ R ² R ³ N (CH ₃ ) ^ρ X ^σ or R ¹ R ² R ³ R ⁴ N ^ρ X ^σ . The radicals R ¹ , R ² , R ³ and R ⁴ may preferably be, independently of one another, unsubstituted alkyl having a chain length of 8 to 24 C atoms, in particular of 10 to 18 C atoms, hydroxyalkyl having 1 to 4 C atoms, phenyl, C ₂ to C ₁₈ alkenyl, C ₇ to C ₂₄ aralkyl, (C ₂ H ₄ O) _x H, where x is from 1 to 3, one or more ester group-containing alkyl groups or cyclic quaternary ammonium salts. X is a suitable anion.

wobei R¹ für eine lineare oder verzweigte, gesättigte oder ungesättigte Alkylgruppe mit 5 bis 22 Kohlenstoffatomen, bevorzugt 8 bis 18 Kohlenstoffatomen, besonders bevorzugt 8 bis 14 Kohlenstoffatomen, R² für eine Methylgruppe, R³ für eine Methylgruppe oder ebenso wie R⁴ für eine Gruppe der Formel -A-(OA)_n-OH steht, wobei A eine -C₂H₄- und/oder -C₃H₆-Gruppe und n eine Zahl von 0 bis 20 sein kann.
X kann jedes beliebige Anion sein, beispielsweise Chlorid, Bromid, Iodid, Fluorid, Sulfat, Hydrogensulfat, Carbonat, Hydrogencarbonat, Acetat, Citrat, Phosphat, Mono- und Di-Hydrogenphosphat, Pyrophosphat, Polyphosphat, Metaphosphat, Nitrat, Methylsulfat, Phosphonat, Methylphosphonat, Methandisulfonat, Methylsulfonat, Ethansulfonat oder für ein Anion der Formeln R⁶SO₃ ^θ, R⁷SO₄ ^θ oder R⁶COO^θ stehen, worin R⁶ und R⁷ C₂-C₂₀-, vorzugsweise C₁₀-C₁₈-Alkyl, und R⁷ zusätzlich auch C₁-C-₁₈-Alkylphenyl bedeuten.Further suitable cationic surfactants are quaternary alkylhydroxyalkylammonium salts according to the formula (6)

wherein R ^{1 is} a linear or branched, saturated or unsaturated alkyl group having 5 to 22 carbon atoms, preferably 8 to 18 carbon atoms, more preferably 8 to 14 carbon atoms, R ^{2 is} a methyl group, R ^{3 is} a methyl group or R ^{4 is} a Group of the formula -A- (OA) _n -OH, where A can be a -C ₂ H ₄ and / or -C ₃ H ₆ group and n can be a number from 0 to 20.
X can be any anion, for example, chloride, bromide, iodide, fluoride, sulfate, hydrogensulfate, carbonate, bicarbonate, acetate, citrate, phosphate, mono- and di-hydrogenphosphate, pyrophosphate, polyphosphate, metaphosphate, nitrate, methylsulfate, phosphonate, methylphosphonate , Methanedisulfonate, methylsulfonate, ethanesulfonate or an anion of the formulas R ⁶ SO ₃ ^θ , R ⁷ SO ₄ ^θ or R ⁶ COO ^θ , where R ⁶ and R ^{7 are} C ₂ -C ₂₀ -, preferably C ₁₀ -C ₁₈ - Alkyl, and R ⁷ additionally also C ₁ -C ₁₈ alkylphenyl mean.

Highly preferred is C _8-10 alkyl quaternary ammonium hydroxyethyl ammonium chloride or methosulfate and C _12-14 alkyl quaternary ammonium hydroxyethyl ammonium chloride or methosulfate.

If the compositions used according to the invention contain one or more cationic surfactants, these are preferably present in an amount of 0.1-15% by weight and more preferably in an amount of 0.5-7% by weight, in each case based on the total weight of the compositions.

When the compositions used in the invention contain one or more cationic surfactants, the weight ratio of the one or more cationic surfactants to the one or more anionic surfactants is preferably from 1 to 10 to 1 to 5.

Suitable bleaching agents are hydrogen peroxide and inorganic persalts, preferably percarbonates, perborates, persulfates and persilicates, in particular in the form of alkali metal salts. Particularly preferred bleaching agents are hydrogen peroxide, sodium perborate (monohydrate and tetrahydrate) and / or Sodium percarbonate, particularly preferably sodium perborate (monohydrate and tetrahydrate) and / or sodium percarbonate.

If the compositions used according to the invention contain one or more of the bleaching agents just mentioned, they must not contain a bleach activator. In this case, they also preferably do not contain a bleach catalyst.

If the compositions used according to the invention comprise one or more bleaching agents, these are preferably present in an amount of from 1 to 25% by weight, more preferably from 5 to 20% by weight and especially preferably from 8 to 16% by weight, in each case on the total weight of the composition.

The compositions used must not contain peracids or their salts.

In a preferred embodiment of the invention, the compositions used in the invention contain no bleach, i. they are free of bleach.

Unless the compositions contain bleach, they may contain one or more bleach activators.

As bleach activators, the compositions according to the invention may contain one or more substances selected from the following group: polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulphonates, in particular n-nonanoyloxy or n-lauroyloxybenzenesulphonate (NOBS or LOBS), acylated phenolcarboxylic acids, in particular nonanoyloxy or decanoyloxybenzoic acid (NOBA or DOBA), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl-caprolactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. In addition, nitrile derivatives such as n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA) or cyanomorpholine (MOR) can be used as bleach activators. Combinations of conventional bleach activators can also be used.

Particularly preferred bleach activators are tetraacetylethylenediamine, decanoyloxybenzoic acid, n-nonanoyloxybenzenesulfonate or n-lauroyloxybenzenesulfonate.

If the compositions according to the invention comprise one or more bleach activators, these are preferably present in an amount of 1-10% by weight, more preferably in an amount of 1-6% by weight and more preferably in an amount of 2-5% by weight. -% ent, each based on the total weight of the composition of the invention.

In a preferred embodiment of the invention, the compositions used in the invention do not contain a bleach activator, i. H. they are free of Bieichaktivator.

In a particularly preferred embodiment of the invention, the compositions used according to the invention contain no bleach and no bleach activator.

Suitable bleach catalysts are preferably bleach-enhancing transition metal salts or complexes of manganese, iron, cobalt, ruthenium, molybdenum, titanium or vanadium. When using Metal salts are especially preferred manganese salts in the oxidation states +2 or +3, for example manganese halides, the chlorides being preferred, manganese sulfates, manganese salts of organic acids such as manganese acetates, manganese acetylacetonates, manganese oxalates and manganese nitrates.

Further preferred complexes of the iron in the oxidation state II or III and the manganese in the oxidation state II, III, IV or IV, which preferably one or more macrocyclic ligand (s) with the donor functions N1 NR, PR, O and / or S included. Preferably, ligands are used which have nitrogen donor functions. Preference is given to transition metal complexes which contain, as macromolecular ligands, 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN), 1,5,9-trimethyl-1. [delta]. [theta] triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (MeMeTACN) and / or 2-methyl-1,4,7- triazacyclononane (Me / TACN) or bridged ligands such as 1,2-bis- (4,7-dimethyl-1,4,7-triazacyclonono-1-yl) ethane (Me4-DTNE) or derivatives of the cyclam or cyclene such as 1 , 8-dimethylcyclam, 1,7-dimethylcycles, 1,8-diethylcyclam, 1,7-diethylcycles, 1,8-dibenzylcyclam and 1,7-dibenzylcycles, as described e.g. In EP 0 458 397 . EP 0458 398 . EP 0 549 272 . WO 96/06154 . WO 96/06157 or WO 2006/125517 but also manganese complexes, as they are EP 1 445 305 . EP 1 520 910 . EP 1 557 457 and WO 2011/095308 are known.

If the compositions used according to the invention contain one or more bleach catalysts, they are preferably present therein in an amount of 0.001 to 2% by weight, based on the total weight of the compositions.

Other ingredients which may be included in the compositions used include inorganic and / or organic builders and co-builders, so-called builders, to reduce the degree of hardness of the water.

These builders may be included in the compositions in proportions of from 5 to 80% by weight. Inorganic builders include for example, alkali metal, ammonium and alkanolammonium salts of polyphosphates such as tripolyphosphates, pyrophosphates and glassy polymeric metaphosphates, phosphonates, silicates, carbonates including bicarbonates and sesquicarbonates, sulfates and aluminosilicates.

Examples of silicate builders are the alkali metal silicates, in particular those having a SiO ₂ : Na ₂ O ratio of between 1.6: 1 and 3.2: 1, and also phyllosilicates, for example sodium layer silicates, as described in US Pat
US 4,664,839 , available from Clariant under the SKS® brand. SKS-6® is a particularly preferred phyllosilicate builder.

Aluminosilicate builders are particularly preferred. These are, in particular, zeolites of the formula Na _z [(AlO ₂ ) _z (SiO ₂ ) _y ] -xH ₂ O. where z and y are integers of at least 6, the ratio of z to y is 1.0 is 0.5 and x is an integer of 15 to 264.

Suitable aluminosilicate-based ion exchangers are commercially available. These aluminosilicates may be of crystalline or amorphous structure, and may be naturally occurring or synthetically produced.

Preferred ion exchangers based on synthetic crystalline aluminosilicates are available under the designation zeolite A, zeolite P (B) (including those described in US Pat EP-A-0 384 070 disclosed) and zeolite X.

Suitable organic builders include polycarboxylic compounds such as, for example, ether polycarboxylates and oxydisuccinates, such as in U.S. Pat US 3,128,287 and US 3,635,830 described. Likewise on "TMS / TDS" equipment from US 4,663,071 to get expelled.

Other suitable builders include the ether hydroxypolycarboxylates, copolymers of acrylic acid with maleic anhydride, maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, the alkali, ammonium and substituted Ammonium salts of polyacetic acids such. Ethylenediaminetetraacetic acid and nitrilotriacetic acid, and polycarboxylic acids such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and their soluble salts.

Citrate-based builders, e.g. As citric acid and its soluble salts, in particular the sodium salt, are preferred polycarboxylic acid, which can also be used together with zeolites and / or phyllosilicates.

Other suitable builders are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S. Pat US 4,566,984 are disclosed.

If phosphorus based builders can be used, various alkali metal phosphates such as sodium tripolyphosphate, sodium pyrophosphate, and sodium orthophosphate can be used. Also, phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates such as those described in U.S. Pat US 3,159,581 .
US 3,213,030 . US 3,422,021 . US 3,400,148 and US 3,422,137 are disclosed.

The compositions used in the invention may contain wash alkalis which raise the pH of the composition. Suitable are carbonates, bicarbonates and silicates, in particular alkali metal carbonates, alkali metal bicarbonates and alkali silicates having a molar ratio SiO ₂ / M ₂ O (M = alkali metal) of 1: 1 to 2.5: 1.

As enzymes conventional enzymes can be used. The compositions used according to the invention preferably comprise one or more enzymes selected from the group consisting of proteases, amylases, mannases, lipases, endolases, pectinases, cellulases, pullinases, cutinases and peroxidases.

Examples of proteases available are Liquanase® Ultra 2.0 XL, BLAP®, Opticlean®, Maxacal®, Maxapem®, Esperase®, Savinase®, Purafect®, OxP and / or Duraxym®.
amylases, for example, Steinzyme® Plus 12L, Termamyl®, Amylase® LT, Maxamyl®, Duramyl® and / or Pruafect® Ox,
Mannasen, for example, Mannaway 4.0 L,
lipases, for example Lipex® 100 L, Lipolase®, Lipomax®, Lumafast® and / or Lipozym®,
on endolases, for example Endolase® 5000L,
on pectinases, for example Pectinex 3X L and / or Pectinex Ultra SPL and on cellulases, for example Carezyme 1000 L and / or Celluclast 1.5 L.

Preferably, the compositions contain at least 0.001% by weight, more preferably 0.01 to 10% by weight, especially preferably 0.1 to 5% by weight and most preferably 1 to 3% by weight of one or more enzymes, each based on the total weight of the compositions.

Sequestering agents available are sodium tripolyphosphate (STPP), ethylenediaminetetraacetic acid (EDTA), salts, nitrilotriacetic acid (NTA), polyacrylate, phosphonate, oxalic acid, salt, citric acid, zeolite, condensed phosphates, carbonates, polycarbonates.

Suitable for soil release polymers (SRPs) are polyesters obtainable by polymerization of the components selected from one or more sulfo-free aromatic dicarboxylic acids and / or their salts, one or more sulfo-containing dicarboxylic acids, one or more compounds of the formula R ¹ O (CHR ² CHR ³ O) _n H, where R ^{1 is} H, a linear or branched alkyl or alkenyl group having 1 to 22 C atoms, preferably for C ₁ -C ₄ alkyl and particularly preferably for methyl, R ² and R ^{3 are} independent each represent hydrogen or an alkyl group having 1 to 4 carbon atoms, preferably hydrogen and / or methyl, and n is a number from 1 to 100, one or more compounds of the formula H- (OCH ₂ CH ₂ ) _m -SO ₃ X, where m is a number from 1 to 100 and X is hydrogen or an alkali metal ion, and one or more crosslinking polyfunctional compounds.

In a preferred embodiment of the invention, the compositions used according to the invention contain one or more soil release polymers. If the compositions contain one or more soil release polymers, they are preferably present in an amount of from 0.1 to 10% by weight and more preferably in an amount of from 0.2 to 3% by weight, based in each case on Total weight of the compositions.

Suitable graying inhibitors are carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose, methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and polyvinyl pyrrolidone.

Also contemplated are dye transfer inhibitors such as polyamine N-oxides such as poly (4-vinylpyridine-N-oxide), e.g. Chromabond S-400, Fa. ISP; Polyvinylpyrrolidone, e.g. Sokalan® HP 50, BASF and copolymers of N-vinylpyrrolidone with N-vinylimidazole and optionally other monomers.

The compositions used may also contain color fixing agents, for example color fixing agents obtained by reacting diethylenetriamine, dicyandiamide and amidosulfuric acid, amines with epichlorohydrin, for example dimethylaminopropylamine and epichlorohydrin or dimethylamine and epichlorohydrin or dicyandiamide, formaldehyde and ammonium chloride, or dicyandiamide, ethylenediamine and formaldehyde or cyanamide with amines and formaldehyde or polyamines with cyanamides and amidosulfuric acid or cyanamides with aldehydes and ammonium salts, but also polyamine N-oxides such as poly (4-vinylpyridine-N-oxide), for. Chromabond S-400, Fa. ISP; Polyvinylpyrrolidone, e.g. B. Sokalan® HP 50, BASF and copolymers of N-vinylpyrrolidone with N-vinylimidazole and optionally other monomers.

The compositions used according to the invention may be complexing agents, for example aminocarboxylates, such as ethylenediaminetetraacetate,
N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediamine tetrapropionate, triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate, cyclohexanediaminetetraacetate, phosphonates, for example azacycloheptanediphosphonate, Na salt, pyrophosphates, etidronic acid (1-hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxyethyne-1,1-diphosphonic acid, acetophosphonic acid) and their salts, aminophosphonates such as ethylenediaminetetrakis (methylenephosphonate), diethylenetriaminepentakis (methylenephosphonate), aminotrimethylenephosphonic acid, cyclodextrins, and polyfunctionally-substituted aromatic complexing agents such as dihydroxydisulfobenzene or ethylenediamine disuccinates.

Cyclic hydrocarbons, such as distyrylbenzenes, distyrylbiphenyls, diphenylstilbenes, triazinylaminostilbenes, stilbenyl-2H-triazoles, for example stilbenzyl-2H-naphthol [1,2-d] triazoles and bis (1,2,3-triazole-2 -yl) stilbenes, benzoxazoles, for example stilbenylbenzoxazole and bis (benzoxazole), furans, benzofurans and benzimidazoles, for example bis (benzo [b] furan-2-yl) biphenyl and cationic benzimidazoles, 1,3-diphenyl-2-pyrazoline, coumarin , Naphthalimides, 1,3,5-2-yl derivatives, methine cyanine and dibenzothiophene-5,5-oxide.

Preference is given to anionic optical brighteners, in particular sulfonated compounds.

Also contemplated are triazinylaminostilbenes, distyrylbiphenyls, and mixtures thereof, 2- (4-styrylphenyl) -2H-naphtho [1,2-d] triazole, 4,4'-bis (1,2,3-triazole-2-) yl) stilbene, aminocoumarin, 4-methyl-7-ethylaminocoumarin, 1,2-bis (benzimidazol-2-yl) ethylene, 1,3-diphenylphrazoline, 2,5-bis (benzooxazol-2-yl) thiophene, 2- Strylnaphtho [1,2-d] oxazole, 2- (4-styryl-3-sulfophenyl) -2H-naphtho [1,2-d] triazole and 2- (stilben-4-yl) -2H-naphthol [ 1,2-d] triazole.

If the compositions used according to the invention comprise one or more optical brighteners, these are preferably present in amounts of from 0.001 to 2% by weight, more preferably in amounts of from 0.002 to 0.8% by weight and particularly preferably in amounts of from 0.003 to 0, 4 wt .-% therein, each based on the total weight of the compositions.

eingesetzt werden, worin R¹ = C₈-C₂₄ n- oder iso-Alkyl, bevorzugt C₁₀-C₁₈ n-Alkyl, R² = C₁-C₄-Alkyl, bevorzugt Methyl, R³ = R¹ oder R², R⁴ = R² oder Hydroxyethyl oder Hydroxypropyl oder deren Oligomere und X^- = Bromid, Chlorid, Jodid, Methosulfat, Acetat, Propionat oder Lactat sind.As softening components quaternary ammonium salts of the type

be used, in which R ¹ = C ₈ -C ₂₄ n- or iso-alkyl, preferably C ₁₀ -C ₁₈ n-alkyl, R ² = C ₁ -C ₄ -alkyl, preferably methyl, R ³ = R ¹ or R ² , R ⁴ = R ² or hydroxyethyl or hydroxypropyl or their oligomers and X ^- = Bromide, chloride, iodide, methosulfate, acetate, propionate or lactate are.

Examples thereof are distearyldimethylammonium chloride, ditallowalkyldimethylammonium chloride, ditallowalkylmethylhydroxypropylammonium chloride, cetyltrimethylammonium chloride or the corresponding benzyl derivatives such as dodecyldimethylbenzylammonium chloride. Cyclic quaternary ammonium salts such as alkyl morpholine derivatives can also be used.

worin R = C₈-C₂₄ n- oder iso-Alkyl, bevorzugt C₁₀-C₁₈ n-Alkyl, X = Bromid, Chlorid, Jodid oder Methosulfat und A = -NH-CO-, -CO-NH-, -O-CO- oder -CO-O- ist.In addition, besides the quaternary ammonium compounds, imidazolinium compounds (1) and imidazoline derivatives (2) can be used.

wherein R = C ₈ -C ₂₄ n- or iso-alkyl, preferably C ₁₀ -C ₁₈ n-alkyl, X = Bromide, chloride, iodide or methosulfate and A = -NH-CO-, -CO-NH-, -O-CO- or -CO-O- is.

A particularly preferred class of compounds are the so-called ester quats. These are reaction products of alkanolamines and fatty acids, which are then quaternized with conventional alkylating or hydroxyalkylating agents.

wobei R-C-O abgeleitet ist von C₈-C₂₄-Fettsäuren, die gesättigt oder ungesättigt sein können. Der Index n liegt im Bereich von 0 bis 10, vorzugsweise im Bereich von 0 bis 3 und besonders bevorzugt im Bereich von 0 bis 1.Examples of esterquats are compounds of the formulas:

wherein RCO is derived from C ₈ -C ₂₄ fatty acids, which may be saturated or unsaturated. The index n is in the range of 0 to 10, preferably in the range of 0 to 3, and more preferably in the range of 0 to 1.

worin

R¹ und R²

unabhängig voneinander C₈-C₂₄ n- oder iso-Alkyl, bevorzugt C₁₀-C₁₈ n-Alkyl,

A

-CO-NH- oder -NH-CO-,

n

1 bis 3, bevorzugt 2, und

m

1 bis 5, bevorzugt 2 bis 4

bedeuten.Further preferred fabric softener raw materials are amidoamines based on, for example, dialkyltriamines and long-chain fatty acids, and their oxethylates or quaternized variants. These compounds have the following structure:

wherein

R ¹ and R ²

independently of one another C ₈ -C ₂₄ n- or iso-alkyl, preferably C ₁₀ -C ₁₈ n-alkyl,

A

-CO-NH- or -NH-CO-,

n

1 to 3, preferably 2, and

m

1 to 5, preferably 2 to 4

mean.

By quaternization of the tertiary amino group may additionally be a radical R ³ , which may be C ₁ -C ₄ alkyl, preferably methyl, and a counterion X, which may be chloride, bromide, iodide or methyl sulfate, are introduced. Amidoaminoethoxylates or their quaternized secondary products are available under the trade names Varisoft® 510, Varisoft® 512, Rewopal® V 3340 and Rewoquat® W 222 LM.

The compositions used in the invention preferably contain dyes and fragrances or perfumes.

Preferred dyes include Acid Red 18 (CI 16255), Acid Red 26, Acid Red 27, Acid Red 33, Acid Red 51, Acid Red 87, Acid Red 88, Acid Red 92, Acid Red 95, Acid Red 249 (CI). 18134, Acid Red 52 (CI45100), Acid Violet 126, Acid Violet 48, Acid Violet 54, Acid Yellow 1, Acid Yellow 3 (CI 47005), Acid Yellow 11, Acid Yellow 23 (CI 19140), Acid Yellow 3, Direct Blue 199 (CI 74190), Direct Yellow 28 (CI 19555), Food Blue 2 (CI 42090), Food Blue 5: 2 (CI 42051: 2), Food Red 7 (CI 16255), Food Yellow 13 (CI 47005) , Food Yellow 3 (CI 15985), Food Yellow 4 (CI 19140), Reactive Green 12, Solvent Green 7 (CI 59040).

Particularly preferred dyes are water-soluble acid dyes, for example, Food Yellow 13 (Acid Yellow 3, CI 47005), Food Yellow 4 (Acid Yellow 23, CI 19140), Food Red 7 (Acid Red 18, CI 16255), Food Blue 2 (Acid Blue 9, CI 42090), Food Blue 5 (Acid Blue 3, CI 42051), Acid Red 249 (CI 18134), Acid Red 52 (CI 45100), Acid Violet 126, Acid Violet 48, Acid Blue 80 (CI 61585), Acid Blue 182, Acid Blue 182, Acid Green 25 (CI 61570),
Acid Green 81.

Water-soluble direct dyes, for example Direct Yellow 28 (CI 19555), Direct Blue 199 (CI 74190) and water-soluble reactive dyes, for example Reactive Green 12, as well as the dyes Food Yellow 3 (CI 15985), Acid Yellow 184 can also be used with preference ,

It is likewise possible with preference to use aqueous dispersions of the following pigment dyes, the concentration of the dye dispersions used for dyeing solutions or dispersions preferably being in the range from 0.1 to 50% by weight, particularly preferably in the range from 1 to 45% by weight. , more preferably in the range of 5 to 40 wt .-%, and most preferably in the range of 10 to 35 wt .-% is.

It is known to the person skilled in the art that the aqueous pigment dispersions contain, in addition to the pigments, dispersants and optionally further auxiliaries, for example biocides.

Suitable pigment dyes are Pigment Black 7 (CI 77266), Pigment Blue 15 (CI 74160), Pigment Blue 15: 1 (CI 74160), Pigment Blue 15: 3 (CI 74160), Pigment Green 7 (CI 74260). , Pigment Orange 5, Pigment Red 112 (CI 12370), Pigment Red 112 (CI 12370), Pigment Red 122 (CI 73915), Pigment Red 179 (CI 71130), Pigment Red 184 (CI 12487), Pigment Red 188 (CI 12467), Pigment Red 4 (CI 12085), Pigment Red 5 (CI 12490), Pigment Red 9, Pigment Violet 23 (CI 51319), Pigment Yellow 1 (CI 11680), Pigment Yellow 13 (CI 21100), Pigment Yellow 154 , Pigment Yellow 3 (CI 11710), Pigment Yellow 74, Pigment Yellow 83 (CI 21108), Pigment Yellow 97.

In a preferred embodiment of the invention, the following pigment dyes are used in the form of dispersions: Pigment Yellow 1 (CI 11680), Pigment Yellow 3 (CI 11710), Pigment Red 112 (CI 12370), Pigment Red 5 (CI 12490), Pigment Red 181 (CI 73360), Pigment Violet 23 (CI 51319), Pigment Blue 15: 1 (CI 74160), Pigment Green 7 (CI 74260), Pigment Black 7 (CI 77266).

In a further preferred embodiment of the invention, water-soluble polymer dyes, for example Liquitint.RTM., Liquitint Blue HP.RTM., Liquitint Blue 65.RTM., Liquitint Patent Blue.RTM., Liquitint Royal Blue.RTM., Liquitint Experimental Yellow 8949- 43.RTM., Liquitint Green HMC.RTM., Liquitint Yellow II.RTM. and mixtures thereof.

As fragrance or perfume, individual fragrance compounds, eg. As the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons are used. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethylacetate, linalylbenzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate. The ethers include, for example, benzyl ethyl ether to the aldehydes z. As the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. The alcohols include anethole, citronellol, eugenol, geranion, linalool, phenylethyl alcohol and terpineol, the hydrocarbons include mainly the terpenes and balsams. Preferably, mixtures of different fragrances are used, which together produce an attractive fragrance.

Perfume oils may also contain natural fragrance mixtures, such as those available from plant or animal sources, e.g. Pine, citrus, jasmine, lily, rose or ylang-ylang oil. Also essential oils of lower volatility, which are mostly used as aroma components, are suitable as perfume oils, eg. B. sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon oil, lime blossom oil and juniper berry oil.

Preferably used are solutions or emulsions of the abovementioned fragrances and perfume oils, which can be prepared by customary methods.

Suitable emulsifiers are adducts of 0 to 30 moles of alkylene oxide, in particular ethylene, propylene and / or butylene oxide, to linear or branched, saturated or unsaturated fatty alcohols having 8 to 22 C atoms, to fatty acids having 12 to 22 C atoms, on alkylphenols having 8 to 15 C atoms in the alkyl group and on sorbitan esters;
(C ₁₂ -C ₁₈ ) fatty acid mono- and diesters of addition products of 0 to 30 moles of ethylene oxide with glycerol;
Glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and optionally their ethylene oxide addition products;
Addition products of 5 to 60 mol, preferably 15 to 60 mol, of ethylene oxide with castor oil and / or hydrogenated castor oil;
Polyol and in particular polyglycerol esters, such as. Polyglycerol polyricinoleate and polyglycerol poly-12-hydroxy stearate.

In addition, it is possible to use anionic emulsifiers, such as ethoxylated and nonethoxylated mono-, di- or tri-phosphoric esters, but also cationic emulsifiers, such as mono-, di- and tri-alkyl quats and their polymeric derivatives.

Also suitable are mixtures of compounds of several of these classes of substances.

Suitable hydrotropes are xylene sulfonates, toluenesulfonates and cumene sulfonates in the form of their potassium or sodium salts or mixtures thereof.

In a preferred embodiment of the invention, the compositions used according to the invention comprise one or more hydrotropes in an amount of 1-10% by weight, preferably in an amount of 1-6% by weight and more preferably in an amount of 2-5% by weight .-%, each based on the total weight of the compositions.

Preferred organic solvents are selected from the group of monohydric or polyhydric alcohols or glycol ethers. The solvents are preferably selected from ethanol, n- or i-propanol, butanol, glycol, propane or butanediol, glycerol, diglycol, propyl- or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, diethylene glycol methyl ether, Di-ethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol-t Butyl ethers, polyglycols, preferably polyethylene glycols, and mixtures of these solvents.

Furthermore, the compositions used according to the invention contain water.

In a preferred embodiment of the invention, the amount of water in the compositions used is 10 to 60 wt .-%, preferably 10 to 40 wt .-% and particularly preferably 10 to 20 wt .-%, each based on the total weight of the compositions.

In a further preferred embodiment of the invention, the amount of water in the compositions used is <10 wt .-%, preferably <8 wt .-%, particularly preferably <6 wt .-% and particularly preferably <5 wt .-%, respectively based on the total weight of the compositions. The minimum amount of water is preferably 3 wt .-%, based on the total weight of the compositions.

The compositions used according to the invention have a pH of preferably 7 to 11, particularly preferably from 7.5 to 10 and particularly preferably from 7.5 to 8.5.

However, it is known to those skilled in the art that the pH of a liquid composition having a water content <40% by weight, based on the total weight of the liquid composition, can not be determined as such for the liquid composition. For liquid compositions with a water content of <40% by weight, a 1% strength by weight aqueous solution of the liquid composition is prepared and from this the pH is determined by customary methods.

Therefore, the above-mentioned pH values for compositions used according to the invention having a water content of 40% by weight or greater (based on the total weight of the compositions according to the invention) apply directly and for compositions having a water content of <40% by weight (based on the total weight the compositions) for a 1% by weight aqueous solution of the composition.

The compositions used according to the invention can advantageously be used in the presence of one or more bleaches for cleaning textiles and in particular for removing bleachable stains on textiles.

The invention therefore relates to the use of one of the above-described compositions in the presence of one or more bleaches for cleaning textiles and, in particular, for removing bleachable stains on textiles.

In the case of the use according to the invention, the compositions used show in particular a significantly greater cleaning power than comparable alkanolamine or alkanolamine salt-containing compositions.

In the use according to the invention, the compositions used may already contain one or more bleaching agents as described above.

In the use according to the invention, the composition used can be combined with one or more bleaching agents which are used separately from the compositions. This may also be the case if the composition used already contains bleach.

However, in a preferred embodiment of the invention, the use takes place such that the composition used does not contain any bleaching agent but is combined in use with one or more bleaching agents.

Bleaching agents which can be combined with the composition according to the invention in the use according to the invention are, on the one hand, compounds which react with bleach activators and form peroxyacids which bleach much more effectively at low temperatures (eg <70 ° C.) than the bleaches alone ,

Suitable bleaching agents are hydrogen peroxide and inorganic persalts, preferably percarbonates, perborates, persulfates and persilicates, in particular in the form of alkali metal salts. Particularly preferred such bleaching agents are hydrogen peroxide, sodium perborate (monohydrate and tetrahydrate) and / or sodium percarbonate, particularly preferably sodium perborate (monohydrate and tetrahydrate) and / or sodium percarbonate.

Bleaching agents which may not be present in the composition according to the invention but which can be combined with the composition in the use according to the invention are, on the other hand, compounds which act without a bleach activator. Suitable such bleaching agents are peracids or their salts.

wobei R für eine Alkylgruppe, Aralkylgruppe, Cycloalkylgruppe, Arylgruppe oder heterocyclische Gruppe, bevorzugt für eine lineare oder verzweigte, substituierte oder unsubstituierte Alkylgruppe, insbesondere bevorzugt für eine Alkylgruppe mit 6 bis 9 Kohlenstoffatomen, steht und X⁺ ein geeignetes Gegenion, bevorzugt ein H⁺, Kalium- oder Natriumion bedeutet. Bevorzugt sind Peroxyhexanoylsäure, Peroxyheptanoylsäure, Peroxyoctanoylsäure, Peroxynonanoylsäure, Peroxydecanoylsäure und deren Salze.Particularly preferred peracids or peracid salts are peroxycarboxylic acids and their salts according to the formula

wherein R represents an alkyl group, aralkyl group, cycloalkyl group, aryl group or heterocyclic group, preferably a linear or branched, substituted or unsubstituted alkyl group, particularly preferably an alkyl group with 6 to 9 carbon atoms, and X ^{+ is} a suitable counterion, preferably an H ⁺ , potassium or sodium ion. Preference is given to peroxyhexanoic acid, peroxyheptanoic acid, peroxyoctanoic acid, peroxynonanoic acid, peroxydecanoic acid and salts thereof.

wobei R für eine Alkylgruppe, Aralkylgruppe, Cycloalkylgruppe, Arylgruppe oder heterocyclische Gruppe, bevorzugt für eine lineare oder verzweigte, substituierte oder unsubstituierte Alkylgruppe, insbesondere bevorzugt für eine Alkylgruppe mit 6 bis 9 Kohlenstoffatomen, steht und X⁺ ein geeignetes Gegenion, bevorzugt H⁺, ein Kalium- oder Natriumion bedeutet.Further particularly preferred peracids or peracid salts are peroxysulfonic acids and their salts according to the formula

wherein R is an alkyl group, aralkyl group, cycloalkyl group, aryl group or heterocyclic group, preferably a linear or branched, substituted or unsubstituted alkyl group, particularly preferably an alkyl group having 6 to 9 carbon atoms, and X ^{+ is} a suitable counterion, preferably H ⁺ , a potassium or sodium ion.

Further particularly preferred peracids or peracid salts are peroxophthalic acids and their salts, phthalimidoperacids and their salts, diperoxycarboxylic acids and their salts or peroxy-sulfuric acids and their salts.

Among the bleaching agents which have no bleach activator, particular preference is given to the peracids or their salts selected from the group consisting of monoperoxyphthalic acid and its salts, N, N-phthalimidoperhexanoic acid (PAP) and its salts, diperazelaic acid and its salts, diperdodecanedioic acid and their salts and monoperoxy-sulfuric acid and their salts, the salts preferably being selected from the sodium and / or potassium salts. Among monoperoxy sulfuric acid and its salts, in particular, the potassium peroxymonosulfate (available under the trade name Caroat) is preferred. In the use according to the invention, the one or more bleaches in an amount of preferably 1 to 25 wt .-%, particularly preferably 5 to 20 wt .-% and particularly preferably 8 to 16 wt .-%, based on the total weight of inventive composition used. The stated amount of bleach is the total amount of bleach used in the present invention resulting from the amount of bleach in the composition used and the amount of bleach added separately from the composition.

The one or more bleaches may be used in the inventive use either without bleach activator or with one or more bleach activators.

In a preferred embodiment of the use according to the invention, this takes place in the presence of one or more bleach activators.

When used according to the invention, the compositions used may already contain a bleach activator as described above.

In the use according to the invention, the composition used can be combined with one or more bleach activators which are used separately from the composition. This may also be the case if the composition already contains bleach activator.

However, in a preferred embodiment of the invention, use is such that the composition employed does not contain a bleach activator but is combined in use with one or more bleach activators.

It is known to the person skilled in the art that the use of bleach activator only makes sense in the presence of bleach.

In a preferred embodiment of the invention bleach activator is used together with bleach in a physical mixture but separate from the liquid composition used. In this preferred embodiment of the invention, the physical mixture of bleach activator and bleach is in solid form at 25 ° C. If, in the use according to the invention, bleach activators are used together with bleach in a physical mixture, the composition used preferably contains neither bleach nor bleach activator.

In a further preferred embodiment of the invention, bleach activator is used separately from bleach and separately from the composition used according to the invention. If, in the use according to the invention, bleach activator is used separately from bleach and separately from the composition according to the invention, the composition according to the invention preferably contains neither bleach nor bleach activator.

In the use according to the invention, the same bleach activators are used which are already mentioned above. The bleach activators listed there as preferred are preferred in the use according to the invention. This applies both in the case where the one or more bleach activators are present in the composition according to the invention and in the case that they are added in the inventive use in addition to the liquid composition used.

If bleach activators are used in the inventive use, they are used in such a way that, based on the total weight of the liquid compositions used, they are preferably in an amount of 1-10% by weight, more preferably in an amount of 1-6 Wt .-% and particularly preferably in an amount of 2-5 wt .-% present. The stated amount of bleach activator is the total amount of bleach activator used in the inventive use, which consists of the amount of bleach activator in the liquid used Composition and added separately from the composition amount of bleach activator.

The wash liquor should have a pH of preferably from 8.0 to 11.0, more preferably from 8.5 to 10.5 and most preferably from 9.0 to 10.0 in order to achieve a sufficient bleaching result. The increase in the pH in the wash liquor can be achieved by wash alkalis, for example sodium carbonate.

The washing temperature is preferably from 20 to 80 ° C, more preferably from 30 to 60 ° C and particularly preferably from 40 to 60 ° C.

The following examples are intended to illustrate the invention without limiting it thereto. All percentages are, unless explicitly stated otherwise, to be understood as percent by weight (% by weight).

Washing tests were carried out with the following formulations.

Formulation A, ethanolamine-containing

composition % By weight (active substance) A Hostapur® SAS 93 20.5 Sec. Sodium paraffin sulfonate B Genapol® OX 070 (Clariant) C _12,15 -oxoalcohol, 7 EO 30.0 C Edenor® K 12-18 8.0 coconut fatty acid KOH (50% by weight in water) water ad 100 Monoethanolamine 5.0 D Genapol® LRO paste (Clariant) Active ingredient: lauryl ether sulfate, 2EO (EO: ethylene oxide unit), Na salt 8.4 Cublen® BIT 121 2.5 phosphonate Texcare® SRN 170 2.0 Nonionic polyester of polypropylene terephthalate, aqueous Leucophor® BOD liq. 0.5 Optical brightener propylene glycol 10.0 e ethanol 2.0 ® enzyme mix 2.0 Novozymes

method of preparation:

1. I Dissolve A in B by heating.
2. II successive addition and dissolution of the components C in I.
3. III successive addition of components D in II.
4. IV Cooling from III to room temperature and addition of E.

Formulation B, ethanolamine-free

composition % By weight (active substance) A Hostapur® SAS 93 20.5 Sec. Sodium paraffin sulfonate B Genapol® OX 070 (Clariant) C _12,15 -oxoalcohol, 7 EO 30.0 C Edenor® K 12-18 8.0 coconut fatty acid KOH (50% by weight in water) water ad 100 D Genapol® LRO paste (Clariant) Active ingredient: lauryl ether sulfate, 2EO (EO: ethylene oxide unit), Na salt 8.4 Cublen® BIT 121 2.5 phosphonate Texcare® SRN 170 2.0 Nonionic polyester of polypropylene terephthalate, aqueous Leucophor® BOD liq. 0.5 Optical brightener propylene glycol 10.0 e ethanol 2.0 ® enzyme mix 2.0 Novozymes

Method of preparation as formulation A

The washing tests were carried out under the following conditions: Washing machine: Miele Novotronic W 927 WPS Program: Hot wash Coloureds Loading: 3 kg Temperature: 40 ° C Wash cycle: 3 times Amount of water: 12 liters

30 g each of Formulation A and B were dissolved in 500 ml of water immediately before addition to the washing machine, and 2 g of TAED, 4 g of sodium percarbonate and 11 g of soda were added to each solution. The resulting formulations are referred to below as Formulation A1 and Formulation B1.

Differences in reflectance ΔR 457 nm from washed versus unwashed cotton fabrics were measured. The measured soiled textiles are available for purchase. The following 6 textiles / stains were measured: CFT BC-1 (tea), CFT BC-3 (low temperature tea), CFT CS-3, (red wine), WFK 10K (coffee), CFT CS-15 (blueberry juice), CFT CS-8 (grass).

Measurement: Device: Elrepho 3000 (Datacolor) Aperture: XLAV Ø 34mm Edge Filter: 400 nm

The measurements were made directly after preparation of the formulations.

In the following Table A, the measured differences of the remission values ΔR 457 nm are listed for all 6 stains. In addition, the sum of the measured differences of the remission values ΔR 457 nm for all 6 stains is listed.

For the measurements, the formulations A1 and B1 were used with the bleaching additives mentioned above. Table A measured ΔR 457 nm values soiling ΔR 457 nm formulation A1 (comparative) ΔR 457 nm Formulation B1 (invention) CFT BC-1 (tea) 9.6 11.1 CFT BC-3 (low temperature tea) 8th 9.5 CFT CS-3 (red wine) 21.7 23.9 WFK 10K (coffee) 32.8 34.8 CFT CS-15 (blueberry juice) 38 39.6 CFT CS-8 (grass) 23.9 25.4 all 6 soiling 134 144

It can be seen from the results in Table A that the monoethanolamine-free liquid formulation B according to the invention, in combination with the bleaching system consisting of sodium percarbonate and TAED, has a better effect on bleachable stains than the monoethanolamine-containing liquid comparative composition A.

Claims (20)

1. The use of a liquid composition having a viscosity of 100 to 20 000 mPas, measured with the Brookfeld LVT-II viscometer at 20 revolutions/minute and at 20°C, comprising

   a) one or more anionic surfactants selected from the group consisting of the surfactant classes of the sulfonates, sulfates, carboxylates and phosphates and the counterions of the anionic surfactants of component a) selected from the group consisting of the cations of sodium, potassium, calcium and magnesium, and

   b) one or more nonionic surfactants selected from the group consisting of the surfactant classes of the alkoxylated fatty alcohols, fatty acid amides, alkoxylated fatty acid amides and alkyl polyglycosides,

   where the total amount of surfactants of components a) and b) is > 50% by weight, based on the total weight of the liquid composition, and where the anionic surfactants of component a) and the nonionic surfactants of component b) are present in the liquid composition in a weight ratio of component a) to component b) of from 3:1 to 1:3 with the proviso that the composition is free from alkanolamines and salts thereof, in the presence of one or more bleaches for cleaning textiles.
2. The use as claimed in claim 1, wherein the liquid composition comprises one or more anionic surfactants of component a) which are selected from secondary paraffinsulfonates.
3. The use as claimed in one or more of claims 1 to 2, wherein the liquid composition comprises one or more anionic surfactants of component a) which are selected from the group consisting of the salts of lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, hydrogenated erucic acid, oleic acid, linoleic acid, linolenic acid and mixtures thereof and the salts of the fatty acids or fatty acid mixtures of natural fats and oils, preferably of coconut oil, soybean oil, rapeseed oil, sunflower oil, canola oil, palm fat oil, palm kernel oil, olive oil and tallow fat.
4. The use as claimed in one or more of claims 1 to 3, wherein the liquid composition comprises one or more nonionic surfactants of component b) which are selected from condensation products of C₁₀- to C₂₀-alcohols with 2 to 18 mol of ethylene oxide per 1 mol of alcohol.
5. The use as claimed in one or more of claims 1 to 4, wherein the liquid composition comprises one or more enzymes selected from the group consisting of proteases, amylases, mannases, lipases, endolases, pectinases, cellulases, pullinases, cutinases and peroxidases.
6. The use as claimed in one or more of claims 1 to 5, wherein the liquid composition comprises one or more soil release polymers.
7. The use as claimed in one or more of claims 1 to 6, wherein the liquid composition comprises water in an amount of < 10% by weight, based on the total weight of the liquid composition.
8. The use as claimed in claim 1, wherein the liquid composition comprises one or more bleaches.
9. The use as claimed in claim 1, wherein the liquid composition comprises no bleach but, upon use, is combined with one or more bleaches.
10. The use as claimed in one or more of claims 1 to 9, wherein the one or more bleaches are selected from the group consisting of sodium perborate (monohydrate and tetrahydrate) and sodium percarbonate.
11. The use as claimed in one or more of claims 1 to 10, wherein the one or more bleaches are used in an amount of 1 - 25% by weight, based on the total weight of the liquid composition.
12. The use as claimed in one or more of claims 1 to 11, wherein it takes place in the presence of one or more bleach activators.
13. The use as claimed in claim 12, wherein the bleach activator is used together with bleach in a physical mixture but separate from the liquid composition, the physical mixture of bleach activator and bleach is present in solid form at 25°C, and the liquid composition comprises neither bleach nor bleach activator.
14. The use as claimed in claim 12, wherein the bleach activator is used separately from bleach and separately from the liquid composition and the liquid composition comprises neither bleach nor bleach activator.
15. The use as claimed in one or more of claims 12 to 14, wherein the one or more bleach activators are selected from the group consisting of tetraacetylethylenediamine, decanoyloxybenzoic acid, n-nonanoyloxybenzenesulfonate and n-lauroyloxybenzenesulfonate.
16. A liquid composition having a viscosity of 100 to 20 000 mPas, measured with the Brookfeld LVT-II viscometer at 20 revolutions/minute and at 20°C, comprising

    a) one of more anionic surfactants selected from the group of the secondary paraffinsulfonates and the counterions of the anionic surfactants of component a) selected from the group consisting of the cations of sodium, potassium, calcium and magnesium, and

    b) one or more nonionic surfactants selected from the group consisting of the surfactant classes of the alkoxylated fatty alcohols, fatty acid amides, alkoxylated fatty acid amides and alkyl polyglycosides,

    where the total amount of surfactants of components a) and b) is > 50% by weight, based on the total weight of the liquid composition, and where the anionic surfactants of component a) and the nonionic surfactants of component b) are present in the liquid composition in a weight ratio of component a) to component b) of from 3:1 to 1:3 with the proviso that the composition is free from alkanolamines and salts thereof, and where the liquid composition comprisies 5-20% by weight of one or more bleaches from the group of hydrogen peroxide and inorganic persalts, based on the total weight of the liquid composition.
17. The liquid composition as claimed in claim 16, wherein it comprises one or more nonionic surfactants of component b) which are selected from condensation products of C₁₀- to C₂₀-alcohols with 2 to 18 mol of ethylene oxide per 1 mol of alcohol.
18. The liquid composition as claimed in claim 16 or 17, wherein it comprises one or more enzymes selected from the group consisting of proteases, amylases, mannases, lipases, endolases, pectinases, cellulases, pullinases, cutinases and peroxidases.
19. The liquid composition as claimed in one or more of claims 16 to 18, wherein it comprises one or more soil release polymers.
20. The liquid composition as claimed in one or more of claims 16 to 19, wherein it comprises water in an amount of < 10% by weight, based on the total weight of the liquid composition.